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991.
Dr. Benjamin C. M. Martindale Georgina A. M. Hutton Prof. Christine A. Caputo Sebastian Prantl Dr. Robert Godin Prof. James R. Durrant Dr. Erwin Reisner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(23):6559-6563
Single-source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g-N-CD) and without (g-CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H2 evolution using g-N-CD (7950 μmolH2 (gCD)−1 h−1) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g-N-CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis. 相似文献
992.
In this paper, we derive an approximation for throughput of TCP Compound connections under random losses. Throughput expressions for TCP Compound under a deterministic loss model exist in the literature. These are obtained assuming that the window sizes are continuous, i.e., a fluid behavior is assumed. We validate this model theoretically. We show that under the deterministic loss model, the TCP window evolution for TCP Compound is asymptotically periodic and is independent of the initial window size. We then consider the case when packets are lost randomly and independently of each other. We discuss Markov chain models to analyze performance of TCP in this scenario. We use insights from the deterministic loss model to get an appropriate scaling for the window size process and show that these scaled processes, indexed by p, the packet error rate, converge to a limit Markov chain process as p goes to 0. We show the existence and uniqueness of the stationary distribution for this limit process. Using the stationary distribution for the limit process, we obtain approximations for throughput, under random losses, for TCP Compound when packet error rates are small. We compare our results with ns2 simulations which show a good match and a better approximation than the fluid model at low p. 相似文献
993.
The impact of macromolecule constitution and electrostatic dimensions on the adsorption of cationic model polyelectrolytes (PELs) onto oppositely charged porous microspheres (MSs) suspended in aqueous media is demonstrated. The contour length (L) of the PEL, the chemical structure of the substituents at the ionic group, the ionic strength of the solution (I), and the average pore radius of the microspheres (R) are considered as variable. Adsorption isotherms quantitatively reveal how PEL parameters, MS geometry, and medium characteristics affect the adsorbed amount and surface coverage. Electrostatic exclusion from pores was proved as long as the Debye length (lD) exceeded R, even if L was considerably smaller than the pore diameter. Two charge parameters (CRcalc and CRexp) and the ratio thereof (CR) were derived and served to evaluate the loading process. All three parameters are applicable to two limiting cases, first, adsorption only on the outer surface of the MS and, second, additional adsorption inside the pores. The findings are seen as valuable contributions to basic research in the field of PELs. Precise data, which were not available before, are provided for comparison with theoretical models and simulations. Overall, conclusions from this model system may be useful for technical applications such as surface modification, chromatographic processes, or materials development. 相似文献
994.
Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element g(xy) was computed to be -0.047 bohr(3) with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions. 相似文献
995.
A detailed analysis of the origins of vibrational frequency shifts of diatomic molecules (I2 and ICl) in a rare gas (Xe) liquid is presented. Specifically, vibrationally adiabatic mixed quantum-classical molecular dynamics simulations are used to obtain the instantaneous frequency shifts and correlate the shifts to solvent configurations. With this approach, important mechanistic questions are addressed, including the following: How many solvent atoms determine the frequency shift? What solvent atom configurations lead to blue shifts, and which lead to red shifts? What is the effect of solute asymmetry? The mechanistic analysis can be generally applied and should be useful in understanding what information is provided by infrared and Raman spectra about the environment of the probed vibrational mode. 相似文献
996.
997.
Muscle wasting, characterized by the loss of protein mass in myofibers, is in most cases largely due to the activation of intracellular protein degradation by the ubiquitin proteasome system (UPS). During the last decade, mechanisms contributing to this activation have been unraveled and key mediators of this process identified. Even though much remains to be understood, the available information already suggests screens for new compounds inhibiting these mechanisms and highlights the potential for pharmaceutical drugs able to treat muscle wasting when it becomes deleterious. This review presents an overview of the main pathways contributing to UPS activation in muscle and describes the present state of efforts made to develop new strategies aimed at blocking or slowing muscle wasting. Publication history: Republished from Current BioData's Targeted Proteins database (TPdb; http://www.targetedproteinsdb.com). 相似文献
998.
A four-folded azidation of tetrakis(4-iodophenyl)methane and -adamantane leads to stable organic azides, but yet energetic materials, measured by differential scanning calorimetry (DSC). The rigid and symmetrical structures can be useful for new polymer and nanomaterial developments in material sciences as well as bioconjugations, after 1,3-dipolar cycloaddition reactions with terminal alkynes to 1,2,3-triazoles. 相似文献
999.
Sandra K Verleysen K Labeur C Vanneste L D'Hondt F Thomas G Kas K Gevaert K Vandekerckhove J Sandra P 《Journal of separation science》2007,30(5):658-668
The previously reported COmbined FRActional DIagonal Chromatography (COFRA-DIC) methodology, in which a subset of peptides representative for their parent proteins are sorted, is particularly powerful for whole proteome analysis. This peptide-centric technology is built around diagonal chromatography, where peptide separations are crucial. This paper presents high efficiency peptide separations, in which four 250 x 2.1 mm, 5 microm Zorbax 300SB-C18 columns (total length 1 m) were coupled at operating temperatures of 60'C using a dedicated LC oven and conventional LC equipment. The high efficiency separations were combined with the COFRADIC procedure. This extremely powerful combination resulted, for the analysis of serum, in an increase in the uniquely identified peptide sequences by a factor of 2.6, compared to the COFRADIC procedure on a 25 cm column. This is a reflection of the increased peak capacity obtained on the 1 m column, which was calculated to be a factor 2.7 higher than on the 25 cm column. Besides more efficient sorting, less ion suppression was noticed. 相似文献
1000.
Biagini RE Parks CG Smith JP Sammons DL Robertson SA 《Analytical and bioanalytical chemistry》2007,388(3):613-618
The purpose of this study was to evaluate the precision and accuracy of a commercial multiplexed kit for the measurement of 9 anti-nuclear antibodies (ANAs; anti-SS/A, anti-SS/B, anti-Sm, anti-RNP, anti-Jo-1, anti-Scl-70, anti-dsDNA, anti-Centromere B, and anti-Histone), and to compare these results to a subset of ANAs measured by enzyme-linked immunosorbent assays (ELISA) and immunodiffusion (ID). Sera were obtained from 22 systemic lupus erythematosus (SLE) patients, twelve controls and five others (commercial source) with various autoimmune diseases. ANA results from the AtheNA MultiLyte ANA II Assay (AtheNA) were compared to ELISA results (controls) and patients (ID). The AtheNA interassay coefficients of variation (CVs, N = 39, performed in duplicate; replicated 3x) ranged from 6.2% to 16.7% (mean = 9.8%), while the intra-assay CVs ranged from 5.8% to 14.3% (mean = 10.8%). Compared to results for SLE cases and controls, the sensitivity of AtheNA ranged from 85.7% to 100% (mean = 97.1%), while diagnostic specificity ranged from 16.7% to 100% (mean = 71.6%). There was significant agreement (P values ranging from 0.0001 to 0.03) when analytes coanalyzed by AtheNA and ELISA/ID were evaluated using Cohen's kappa (kappa values ranging from 0.376 to 1.000). No false positive ANA results were observed for either the control or commercial source autoimmune disease sera. These results indicate that the AtheNA assay is a precise and accurate alternative for performing multiple ELISAs or IDs in the diagnosis of autoimmune diseases, especially when the number of sera to be tested is large, such as in clinical screening or epidemiologic studies. It also appears that the AtheNA assay identifies positive ANA specificities which are missed by ID techniques, suggesting that it may have greater analytical sensitivity for some ANAs. 相似文献